Inorganic Metal Chalcogen Cluster Precursors and Methods for Forming Colloidal Metal Chalcogenide Nanoparticles Using the Same

ABSTRACT

Methods for forming colloidal metal chalcogenide nanoparticles generally include forming soluble inorganic metal chalcogen cluster precursors, which are then mixed with a surfactant and heated to form the colloidal metal chalcogenide nanoparticles. The soluble inorganic metal chalcogen cluster precursors are generally formed using a hydrazine-based solvent. The methods can be used with main group and transition metals.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. Ser. No.11/757,056 filed Jul. 20, 2007, the contents of which are incorporatedby reference herein in their entirety.

TRADEMARKS

IBM® is a registered trademark of International Business MachinesCorporation, Armonk, N.Y., U.S.A. Other names used herein may beregistered trademarks, trademarks or product names of InternationalBusiness Machines Corporation or other companies.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to inorganic metal chalcogen clusterprecursors and methods for forming colloidal metal chalcogenidenanoparticles using the inorganic metal chalcogen cluster precursors.

2. Description of Background

Metal chalcogenides are a range of compounds that contain a metal and aGroup VI element such as sulfur, selenium, or tellurium. These compoundsmay be in binary, ternary, or quaternary form. Colloidal nanoparticlesformed of the metal chalcogenides have been used to fabricate a widerange of optical and electronic devices including light emitting diodes,solar cells, optical recording media (phase change), thin filmtransistors, and the like. These materials have also been used asluminescent “tags” for biological labeling and have exhibited lasing andother nonlinear optical effects. Colloidal metal chalcogenidenanoparticles have been synthesized by mixing, in solution, precursorscontaining the metal element(s) with a precursor containing thechalcogen element and at least one surfactant that provides fordispersion in the solution. A controlled precipitation reaction occurs,wherein the various different precursors react to form the metalchalcogenide nanoparticles and the surfactant coats the particle surfaceto limit growth. The precipitation reaction normally requires hightemperatures (e.g., temperatures of 250 to 360° C.) in order todecompose the precursors, overcome the energetic barrier to nucleation,and form nanoparticles, particularly if crystalline nanoparticles aredesired,

Some of the known problems with the co-precipitation route tonanoparticie synthesis include, but are not limited to, the hightemperatures noted above that are needed to initiate the reactionbetween the decomposing precursors (i.e., the reaction between the metalprecursor and the chalcogen precursor) and that suitable precursorcombinations must be discovered that are both soluble in the reactionmixture and that decompose at a sufficiently low temperature, i.e., attemperatures below at or below the boiling point of the solvent. While afew chalcogen precursors have been found suitable for a wide range ofmetal chalcogenides, a suitable precursor must be discovered for eachnew metal to be used. This has led to extensive development ofnanoparticie synthesis for certain metals such as cadmium (Cd), zinc(Zn), or mercury (Hg), with limited success in using analogous syntheticmethods for other metal chalcogenides. In some cases, it has provendifficult to identify conditions and precursors for the preparation ofcertain desirable metal chalcogenide nanoparticles using theco-precipitation process described above.

Another process for forming colloidal metal chalcogenide nanoparticlesincludes the use of a so-called single-source precursor. Single-sourceprecursors are generally molecular precursors with the desired bondsalready formed prior to the nanoparticie synthesis. This type ofprecursor can allow for the formation of nanoparticles with compositionsthat may be difficult to make and/or control through the traditionalco-precipitation route, which involves bond making and breaking.Single-source precursors can also have the advantage of being morestable than their reagent counterparts. An air-stable precursor for thesynthesis of cadmium and zinc sulfide/selenide nanoparticles has beenreported, whereas the prior syntheses of these nanoparticles involvedair-sensitive compounds. Another benefit of single-source precursors isthat they can allow for synthesis of nanoparticles from relativelyharmless reagents.

One disadvantage with single source precursors is that the synthesis ofcurrently known precursors often involves highly reactive/toxic reagentsand can be quite complex. As a result, the precursors arecompositionally specific to the desired nanoparticles. A good example isthe use of single-source precursors to synthesize CdSe nanoparticles.For example, some researchers have used diselenocarbamato cadmiumcomplexes whereas others have used metal-chalcogenide thiophenolateclusters to synthesize the particles. Even more recently, the use of athiocarbamoyl hydrazine cadmium complex for CdSe nanoparticle synthesishas been reported. In all of these syntheses, the precursor used canonly make one type of nanoparticle. If nanoparticles with differentcharacteristics, surfactants or composition are desired, the precursormust be completely redesigned and remade.

Accordingly, there is a need for a different class of single-sourceprecursors suitable for the synthesis of colloidal metal chalcogenidenanoparticles in order to overcome the limitations of existingsingle-source precursor and expand the possibilities for synthesis ofmetal chalcogenide nanoparticles.

SUMMARY OF THE INVENTION

Exemplary embodiments include a method for forming colloidal metalchalcogenide nanoparticles comprising combining a hydrazine-basedinorganic metal chalcogen cluster single source precursor and asurfactant in a solution; and heating the solution to a temperatureeffective to decompose the hydrazine-based inorganic metal chalcogensingle source precursor and form the colloidal metal chalcogenidenanoparticles.

Further exemplary embodiments include a method comprising combining apreheated surfactant-containing solution with an inorganic metalchalcogen cluster single source precursor solution, wherein thepreheated surfactant-containing solution is at a temperature effectiveto decompose the inorganic metal chalcogen single source precursor andform the colloidal metal chalcogenide nanoparticles.

Additional exemplary embodiments include a method comprising dissolvinga soluble, first precursor in a solvent to form a first precursorsolution, wherein the first precursor is inorganic and includesmetal-chalcogen clusters; combining the first precursor solution with asurfactant or a surfactant solution to form a first mixture; formingfrom said first precursor an organometallic second precursor thatincludes the metal-chalcogen clusters to form a second mixture; andheating the organometallic second precursor to decompose themetal-chalcogen clusters, thereby forming the colloidal metalchalcogenide nanoparticles.

Additional features and advantages are realized through the techniquesof the present invention. Other embodiments and aspects of the inventionare described in detail herein and are considered a part of the claimedinvention. For a better understanding of the invention with advantagesand features, refer to the description and to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter that is regarded as the invention is particularlypointed out and distinctly claimed in the claims at the conclusion ofthe specification. The foregoing and other objects, features, andadvantages of the invention are apparent from the following detaileddescription taken in conjunction with the accompanying drawings inwhich:

FIG. 1 is a transmission electron micrograph of GeSe_(x) nanoparticlesproduced in accordance with the present invention;

FIG. 2; is a high resolution transmission electron micrograph ofGeSe_(x) nanoparticles produced in accordance with the presentinvention; and

FIG. 3 graphically illustrates overlayed UV-Vis spectra for a GeSe_(x)reaction mixture taken at different reaction times during formation ofGeSe_(x) nanoparticles prepared in accordance with the presentinvention.

The detailed description explains the preferred embodiments of theinvention, together with advantages and features, by way of example withreference to the drawings.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a process for forming colloidal metalchalcogenide nanoparticles using soluble inorganic precursors containingmetal-chalcogen clusters as a single-source precursor. In oneembodiment, the process generally includes combining a hydrazine-basedinorganic metal chalcogen cluster single source precursor and asurfactant in a solution; and heating the solution to a temperatureeffective to decompose the hydrazine-based inorganic metal chalcogencluster single source precursor and form the colloidal metalchalcogenide nanoparticles

As used herein, the term “inorganic metal-chalcogen cluster” generallyrefers to a group of at least two and not more than twenty atoms thatinclude at least one chalcogen atom, at least one non-chalcogen metalatom and at least one metal to chalcogen chemical bond with the provisothat the cluster is in solution. In the solid phase, one of skill in theart will appreciate that infinite numbers of chains may form betweenclusters. In one embodiment, the inorganic metal-chalcogen cluster isfree of carbon. The term “colloidal metal chalcogenide nanoparticles” asused herein refers to particles of inorganic metal-chalcogen clustersthat are coated with surfactant and have an average diameter of 1nanometer (nm) to 100 nm. In one embodiment, the inorganic particleshave an average diameter of 1 nm to 20 nm. The surfactant-coatedinorganic particles are capable of forming a colloidal dispersion whendispersed in another substance. The method generally includes dissolvingthe inorganic metal-chalcogen cluster precursors) in a suitable solventto form a precursor solution, combining the precursor solution with asurfactant or a surfactant-containing solution, and then heating thismixture to decompose the precursor and produce colloidal metalchalcogenide nanoparticles.

In various embodiments, the precursor solution may be combined with thesurfactant prior to heating or added to a pre-heated surfactant of asurfactant-containing solution in order to control the size and sizedistribution of the resulting metal chalcogenide nanoparticles. In theseembodiments, the mixture of the precursor solution and the surfactant ismaintained at a temperature effective to decompose the metal chalcogenprecursor in the solution and thereby form colloidal metal chalcogenidenanoparticles in the solution. Once the mixture is cooled, thenanoparticles are optionally separated as in other methods for isolatingnanoparticles. For example, the nanoparticles can be purified by washingin a solvent/non-sol vent pair such as hexane/methanol and recoveredfrom the solution by centrifugation. The isolated colloidal metalchalcogenide nanoparticles remain coated with the surfactant and cantherefore be re-dispersed into a variety of organic solvents for furtherprocessing into a variety of devices and applications.

Optionally, the inorganic metal-chalcogen cluster precursor may becombined with a surfactant or surfactant solution to form anorganometallic metal-chalcogen cluster precursor, which may optionallybe isolated and utilized in a similar manner to that described above toform the colloidal metal chalcogenide nanoparticles. The term“organometallic metal-chalcogen cluster precursor” refers to a compoundcontaining metal-chalcogen clusters as generally defined above andincluding at least one hydrocarbon component chemically bonded (ionic,covalent, dative, or other type of chemical bond) to at least one atomincluded in the metal-chalcogen cluster. If the organometallic precursoris not isolated, this mixture can be heated as in the case of theinorganic metal-chalcogen cluster precursor to decompose the precursorand form the metal chalcogenide nanoparticles. If the organometallicprecursor is isolated, then it is dissolved to form a precursorsolution, which is then combined with a surfactant, orsurfactant-containing solution, in the same way as described for theinorganic metal-chalcogen precursor and heated to form thenanoparticles.

The metal chalcogenide as used herein includes a metal, such as, Ge, Sn,Pb, Sb, Bi, Ga, In, Tl, Cu, or a combination thereof and a chalcogen,such as, S, Se, Te or a combination thereof. In one embodiment, themetal chalcogenide can be represented by the formula MX or MX₂, whereinM is the metal and X is the chalcogen. In another embodiment, the metalchalcogenide can be represented by the formula M₂X₃, wherein M is ametal, such as, Sb, Bi, Ga, In or a combination thereof and wherein X isa chalcogen, such as, S, Se, Te or a combination thereof. In yet anotherembodiment, the metal chalcogenide can be represented by the formula M₂Xwherein M is Tl and wherein X is a chalcogen, such as, S, Se, Te or acombination thereof.

A preferred procedure for forming the inorganic metal-chalcogen clusterprecursor for processing is carried out by dissolving a metal chalcogenin a hydrazine-based solvent and stirring to produce a solutioncontaining a hydrazine-based metal chalcogenide precursor. Optionally,an elemental chalcogen, such as, S, Se, Te or a combination thereof canbe added. The excess hydrazine solvent is then removed by evaporation,for example, to leave a solid hydrazine-based inorganic metal-chalcogencluster precursor.

Exemplary hydrazine compounds are represented by the formula: R¹R²N—NR³R⁴, wherein each of R¹, R², R³ and R⁴ is independently hydrogen,aryl, methyl, ethyl or a linear, branched or cyclic alkyl of 3-6 carbonatoms. Preferably, in this method each of R¹, R², R³ and R⁴ isindependently hydrogen, aryl, methyl or ethyl. More preferably, thehydrazine compound is hydrazine, i.e., where R¹, R², R³ and R⁴ are allhydrogens, methylhydrazine or 1,1-dimethylhydrazine.

In another embodiment, a procedure for forming the inorganicmetal-chalcogen cluster precursor includes contacting the metalchalcogen with a salt of an amine to produce an ammonium-based precursorof the metal chalcogenide, wherein the amine compound is represented bythe formula: NR⁵R⁶R^(7,) wherein each of R⁵, R⁶, and R⁷ is independentlyhydrogen, aryl such as phenyl, a linear or branched alkyl having 1-6carbon atoms such as methyl, ethyl or a cyclic alkyl of 3-6 carbonatoms. The ammonium-based precursor of the metal chalcogenide is thencontacted with a hydrazine compound and optionally, an elementalchalcogen. By way of example, the method includes contacting at leastone metal chalcogenide and a salt of an amine compound with H₂S, H₂Se orH₂Te to form an ammonium-based precursor of the metal chalcogenide,contacting the ammonium-based precursor with a hydrazine compound asnoted above to produce a solution of a hydrazinium-based precursor ofthe metal chalcogenide in the hydrazine compound.

In these embodiments, each of R¹, R², R³R⁴, R⁵, R⁶ and R⁷ canindependently be hydrogen, aryl such as phenyl, alkyl having 1-6 carbonatoms such as methyl and ethyl. More typically, R¹, R², R³, R⁴, R⁵, R⁶and R⁷ can independently be hydrogen, aryl, methyl and ethyl. Moretypically R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are all hydrogens.

Typically, the amine compound is NH₃, CH₃ NH₂, CH₃CH₂NH₂, CH₃CH₂CH₂NH₂,(CH₃)₂CHNH₂, CH₃CH₂CH₂CH₂NH₂, phenethylamine, 2-fluorophenethylamine,2-chlorophenethylamine, 2-bromophenethylamine, 3-fluorophenethylamine,3-chlorophenethylamine, 3-bromophenethylamine, 4-bromophenethylamine,2,3,4,5,6-pentafluorophenethylamine or a combination thereof.

The ammonium metal chalcogenide precursor can be prepared by a varietyof techniques depending on the metal chalcogenide under consideration.Examples of such techniques include simple dissolution of the metalchalcogenide in an ammonium chalcogenide aqueous solution followed byevaporation of the solvent, typically at room temperature, solvothermaltechniques and by solid-state routes at elevated temperatures. Incontrast to most metal chalcogenides, which are not substantiallysoluble in common solvents, the ammonium salts can be highly soluble incommon solvents.

Using these techniques, tertiary or higher order systems, (such asSnS_(2-x)Se_(x)) can also be conveniently formed as nanoparticles,enabling more detailed control over the band gap of the materialsdeposited. Thus, the present invention can be used most advantageouslyto form colloidal nanoparticles of main-group metal (e.g., Ge, Sn, Pb,Sb, Bi, Ga, In, Tl) and transition group metals.

The so-formed metal chalcogen cluster precursor is then mixed with asurfactant (neat or in solution) and subsequently heated to atemperature effective to decompose the precursor and form the colloidalmetal chalcogenide nanoparticles.

Suitable surfactants that can be used include aliphatic carboxylicacids, fatty carboxylic acids, unsaturated carboxylic acids,n-alkylphosphonic acids, primary alkylamines, secondary alkylamines,tertiary alkylamines, alkylphosphines, alkylphosphine oxides, all havingfrom 1 to about 30, more preferably from about 6 to about 20 carbonatoms, and functionalized polymers, or any combination of these.Aliphatic carboxylic acids and alkylamines are preferred with aliphaticcarboxylic acids most preferred. Illustrative examples of aliphaticcarboxylic acids that can be employed in the present invention include,for example, caprylic acid, capric acid, lauric acid, myristic acid,palmitic acid, stearic acid, oleic acid, linoleic acid, and other likealiphatic carboxylic acids, including mixtures thereof. Some othernon-limiting examples of surfactants that can be employed in the presentinvention include fatty carboxylic acids (such as lauric, myristic,palmitic and stearic acids), unsaturated carboxylic acids (such aselatic and oleic acids), 1-adamantanecacboxylic acid, n-alkylphosphonicacids (such as n-hexylphosphonic, n-octylphosphonic, n-decylphosphonic,n-tetradecylphosphonic and n-octadacylphosphonic acids), primary alkylamines (such as octylamine, dodecylamine, hexadecylamine, octadecylamineand oleyl amine), secondary alkyl amines (such as dioctylamine),tertiary alkylamines (such as trioctylamine), alkyl phosphines (such astri-n-octylphosphine and tri-n-butylphosphine), alkyl phosphine oxides(such as tri-n-octylphosphine), fluorinated fatty carboxylic acids,fluorinated alkyl phosphines, functionalized polymers (such aspoly(1-vinylpyrrolidone)-graft-(1-hexadecene)), mixtures of theforegoing, and the like.

The amount of surfactant added to the metal chalcogen cluster precursormay vary and is not believed to be critical to the present invention soas long as a sufficient amount of surfactant is employed which can serveas a passivation layer for the subsequently formed colloidalnanoparticles. The term “passivation layer” is used in the presentinvention to denote a medium in which the surface of the nanoparticlesis covered by a monolayer of amphiphilic species which ideally help topassivate dangling bonds at the surface and also provide a stericcolloidal stabilization that prevents the particles from aggregatingirreversibly. Typically, the surfactant is employed in the presentinvention in an amount to provide a ratio of surfactant to firstprecursor from about 1:2 to about 1:50. More specifically, thesurfactant is employed in the present invention in an amount to providea ratio of surfactant to first precursor from about 1:3 to about 1:6.

If a surfactant-containing solution is used, the surfactant orcombination of surfactants is dissolved in an organic solvent that isinert with the precursor and/or any other components used to form thecolloidal nanoparticles (i.e., doesn't react). In one embodiment, thesolvent for the surfactant solution is selected to have a boiling pointgreater than about 100° C. The solvent may include ethers (such asbenzyl ether, phenyl ether, or octyl ether), alkanes or alkenes (such as1-octadecene, squalane, or octadecane), alcohols or diols (such as1,2-hexadecandiol), or other solvents meeting the criteria listedincluding a combination of solvents.

When the mixture of the precursor solution and surfactant orsurfactant-containing solution is heated to decompose the precursor itwill preferably be heated to a temperature above 80° C. and not morethan 400° C., and in other embodiments, between 80° C. and 250° C. Ifthe precursor solution is mixed with the surfactant or surfactantsolution prior to heating, the heating is carried out at a controlledrate between 0.1 and 120 degrees Kelvin per minute (K/min), preferablybetween 1 and 10 K/min.

The solvent used to dissolve the hydrazine-based metal chalcogenideprecursor or the ammonium based metal chalcogenide precursor is anysolvent that dissolves the precursor. In one embodiment, the precursorsolvent has a solubility limit of at least 5 mg/mL. It is preferred thatthe precursor solvent be miscible with the surfactant or with thesurfactant solution at the temperature of nanoparticie nucleation andgrowth. Suitable non-limiting examples include ethanolamine,dimethylsulfoxide, dimethylformamide, N-methylformamide,1-methylimidazole, any hydrazine compound (such as hydrazine or analkylhydrazine), or a combination of these.

The following non-limiting example is presented to better illustrate thepresent disclosure.

EXAMPLE

In this example, GeSe_(x) nanoparticles were prepared using an inorganicGe—Se cluster precursor. To prepare the precursor, equimolar amounts ofGe(II)Se and Se were dissolved into distilled hydrazine (N₂H₄). Afterall of the Ge(II)Se and Se solids were dissolved in the hydrazine, theexcess hydrazine solvent was evaporated off leaving a red, glassy solid.To prepare the nanoparticles, 70 milligrams (mg) of the above describedprecursor were dissolved into 3 milliliters (mL) of ethanolamine andinjected into 5 mL of ethylhexanoic acid at 200° C. under flowingnitrogen. The reaction was maintained at 200° C. for a period of 2 to 40minutes. The variation in reaction time provided different particlesizes with the longer reaction time providing the largest particlesizes. After cooling the reaction mixture to room temperature, excessethanol was added to precipitate the nanoparticles. The nanoparticles soobtained were soluble in various non-polar solvents (e.g., toluene,chloroform), and were re-precipitated in ethanol in order to eliminateexcess surfactant.

FIG. 1 shows a transmission electron micrograph (TEM) micrograph ofnanoparticles made from the inorganic Ge—Se cluster precursor. Thenanoparticles were approximately 5 nm in diameter and well dispersed. Asshown in FIG. 2, high-resolution TEM showed lattice fringes on thenanoparticles, which are characteristic of a crystalline orpolycrystalline phase. Nanoparticle growth was monitored usingultraviolet-visible (UV-Vis) spectroscopy via the characteristic firstexiton peak. FIG. 3 shows UV-Vis spectra as a function of reaction time.As the reaction time increased, the peak shifted towards longerwavelengths indicating nanoparticle growth.

Advantageously, the methods of producing metal chalcogenidenanoparticles using the inorganic metal chalcogen single sourceprecursors have several advantages over previously known methods. First,the inorganic metal-chalcogen precursors, and especially those which arehydrazine-based, contain unique metal-chalcogen combinations that havepreviously been difficult to prepare or unknown in colloidalnanoparticles so that this method expands the materials that can beprepared as metal chalcogenide nanoparticles. Second, like othersingle-source precursor routes to colloidal nanoparticles, but unlikethe more common routes which use separate metal and chalcogenprecursors, the single source precursors contain pre-formedmetal-chalcogen bonds. This allows the formation of crystallinenanoparticles (for that matter, any kind of nanoparticle) at lowertemperatures than is normally possible using the common approach. Suchprecursors are particularly known for their low decompositiontemperatures making the entire class of compounds potentially suitablefor synthesizing nanoparticles in the solution phase. The combination ofthese benefits provides a route to crystalline nanoparticles that,cannot currently be prepared by any other means. Unlike othersingle-source precursors to nanoparticles, these precursors can be madeby a general strategy, using exceptionally simple methods. Thesecharacteristics of the inorganic metal-chalcogen cluster precursors makethe disclosed method more versatile for the preparation of a wide rangeof metal chalcogenide materials than other single source precursormethods.

While the preferred embodiment to the invention has been described, itwill be understood that those skilled in the art, both now and in thefuture, may make various improvements and enhancements which fall withinthe scope of the claims which follow. These claims should be construedto maintain the proper protection for the invention first described.

1. A method for forming colloidal metal chalcogenide nanoparticles,comprising: combining a hydrazine-based inorganic metal chalcogencluster single source precursor and a surfactant in a solution; andheating the solution to a temperature effective to decompose thehydrazine-based inorganic metal chalcogen cluster single sourceprecursor and form the colloidal metal chalcogenide nanoparticles. 2.The method of claim 1, wherein the hydrazine-based metal chalcogencluster single source precursor is formed by a process comprising:dissolving a metal and a chalcogen or a combination of chalcogens in ahydrazine solvent; and removing substantially all of the solvent to formthe hydrazine-based inorganic metal chalcogen cluster single sourceprecursor.
 3. The method of claim 2, wherein the hydrazine solvent isrepresented by the formula:R¹R²N—NR³R⁴, wherein each of R¹, R², R³ and R⁴ is independently selectedfrom the group consisting of hydrogen, aryl, methyl ethyl, linear alkylof 3-6 carbon atoms, branched alkyl of 3-6 carbon atoms and cyclic alkylof 3-6 carbon atoms.
 4. The method of claim 2, further comprising addinga second chalcogen or combination of chalcogens to the hydrazine-basedinorganic metal chalcogen cluster single source precursor prior toheating.
 5. The method of claim 2, wherein the hydrazine-based metalchalcogen cluster single source precursor is formed by a processcomprising: contacting a metal chalcogenide with a salt of an amine toproduce an ammonium-based precursor of the metal chalcogenide; andcontacting the ammonium-based precursor with the hydrazine solvent toproduce a solution of a hydrazinium-based precursor of the metalchalcogenide in the hydrazine solvent.
 6. The method of claim 1, whereinthe hydrazine-based inorganic metal chalcogen cluster single sourceprecursor comprises at least two and not more than twenty atoms, whereinthe atoms comprise at least one chalcogen atom, at least onenon-chalcogen metal atom and at least one metal-to-chalcogen chemicalbond with the proviso that the precursor is in solution.
 7. The methodof claim 1, wherein heating the solution to the temperature effective todecompose the hydrazine-based inorganic metal chalcogen single sourceprecursor is within a temperature range of 80 to 400° C.
 8. The methodof claim 1, wherein the hydrazine-based inorganic metal-chalcogencluster single source precursor is free of carbon.
 9. The method ofclaim 1, wherein the hydrazine-based inorganic metal chalcogen clustersingle source precursor comprises at least one metal selected from thegroup consisting of Cd, Ge, Sn, Pb, Sb, Bi, Ga, In, and Tl and thechalcogen comprises at least one chalcogen selected from the groupconsisting of S, Se, and Te.
 10. The method of claim 1, wherein thesurfactant is selected from the group consisting of an aliphaticcarboxylic acid, an alkylphosphine, an alkylphosphine oxide, analkylamine, a functionalized polymer, and mixtures thereof.
 11. Themethod of claim 1, wherein the solution comprises a solvent having aboiling point greater than 100° C.
 12. A method for forming colloidalmetal chalcogenide nanoparticles, comprising: combining a preheatedsurfactant-containing solution with an inorganic metal chalcogen clustersingle source precursor solution, wherein the preheatedsurfactant-containing solution is at a temperature effective todecompose the inorganic metal chalcogen single source precursor and formthe colloidal metal chalcogenide nanoparticles.
 13. The method of claim12, wherein the inorganic metal chalcogen cluster single sourceprecursor solution is formed by a process comprising: dissolving a metaland a chalcogen or combination of chalcogens in a hydrazine solvent; andremoving substantially all of the solvent to form the hydrazine-basedinorganic metal chalcogen cluster single source precursor.
 14. Themethod of claim 13, wherein the hydrazine solvent is represented by theformula:R¹R²N—NR³R⁴, wherein each of R¹, R², R³ and R⁴ is independently selectedfrom the group consisting of hydrogen, aryl, methyl ethyl, linear alkylof 3-6 carbon atoms, branched alkyl of 3-6 carbon atoms and cyclic alkylof 3-6 carbon atoms.
 15. A method of forming colloidal metalchalcogenide nanoparticles, comprising dissolving a soluble, firstprecursor in a solvent to form a first precursor solution, wherein thefirst precursor is inorganic and includes metal-chalcogen clusters;combining the first precursor solution with a surfactant or a surfactantsolution to form a first mixture; forming from said first precursor anorganometallic second precursor that includes the metal-chalcogenclusters to form a second mixture; and healing the organometallic secondprecursor to decompose the metal-chalcogen clusters, thereby forming thecolloidal metal chalcogenide nanoparticles.
 16. The method of claim 15,wherein the first precursor is formed by a process comprising:dissolving a metal and a chalcogen or combination of chalcogens in ahydrazine solvent; and removing substantially all of the solvent. 17.The method of claim 16, wherein the hydrazine solvent is represented bythe formula:R¹R²N—NR³R⁴, wherein each of R¹, R², R³ and R⁴ is independently selectedfrom the group consisting of hydrogen, aryl, methyl ethyl, linear alkylof 3-6 carbon atoms, branched alkyl of 3-6 carbon atoms and cyclic alkylof 3-6 carbon atoms.
 18. The method of claim 15, further comprisingisolating the nanoparticles.
 19. The method of claim 15, wherein thesurfactant or the surfactant solution is heated prior to being combinedwith the first precursor solution.
 20. The method of claim 15, whereinthe surfactant is an aliphatic carboxylic acid or an alkylamine.